Abstract
Thermal decomposition of the oxygenated fuel component tert-amyl methyl ether (TAME) has been studied by flash pyrolysis up to 1250 K in a 20–100 μs time scale. Pyrolysis was followed by supersonic expansion to isolate intermediates and products, which are monitored by vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS). The species detected, such as CH 3, C 2H 4, C 2H 5, C 4H 8, C 5H 10, C 3H 6O, and C 4H 8O, show competition between molecular elimination and bond fission pathways. The alkenes 2-methyl-1-butene ( 1) and 2-methyl-2-butene ( 2), the primary molecular elimination products of TAME, were separately pyrolyzed to evaluate the extent of secondary decompositions, as were the ketones (acetone and 2-butanone) produced by losses of two alkyl radicals. While vicinal elimination of methanol from TAME to form 1 and 2 in an approximate 3:1 ratio begins around 600 K and continues to dominate at higher temperatures, homolysis of TAME to form radicals onsets >825 K, yielding more acetone than 2-butanone. Contributions from secondary dissociations of the ketone and alkene products are evaluated.
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